N-acyl derivatives of phosphoroamidothioates

ABSTRACT

N-acyl derivatives of O-alkyl-S-aliphatic hydrocarbyl phosphoroamidothioates and S-alkyl-S-aliphatic hydrocarbyl phosphoroamidothioates. These compounds are insecticidal.

United States Patent Magee 1 Feb. 13, 1973 N-ACYL DERIVATIVES OF [56] References Cited PHOSPHOROAMIDOTHIOATES UNITED STATES PATENTS [75] lnvenm" Philip Mag, Rafael Calif- 3,201,446 8/1965 Tolkmith ..260/959 [73] Assignee: Chevron Research Company, San

Francisco, Cam FOREIGN PATENTS OR APPLICATIONS [22] Filed: Feb 24, 1970 253,483 4/1970 U.S.S.R ..260/455 P [21] Appl. No.: 13,846 OTHER PUBLICATIONS Almasi et al., Chem. Ber., Vol. 100, pp. 2625-2632 7 1967 Related US. Application Data [63] Continuation-in-part of Ser. No. 810,383, March 25, Primary Examiner-Lewis Gotts 1969, abandoned. Assistant ExaminerAnton H. Sutto Attorney-G. F. Magdeburger, John Stoner, Jr., J. A. [52] [1.8. CI. ..260/959, 260/294.8 K, 260/326.82, Buchanan and Raymon Owyang P, 260/944, 260/947, 260/948, 260/949, [57] ABSTRACT 260/950, 260/951, 260/954, 260/955, 260/956, 260/958, 260/968, 260/984, N-acyl derivatives of O-alkyl-S-aliphatic hydrocarbyl 424/200, 424/202, 424/203, 424/212 phosphoroamidothioates and S-alkyl-S-aliphatic [51] Int. Cl. ..C07f 9/24, AOln 9/36 hydrocarbyl phosphoroamidothioates. These com- [58] Field of Search ..260/959, 944, 402.5, 956 pounds are insecticidal.

12 Claims, No Drawings N-ACYL DERIVATIVES F PHOSPIIOROAMIDOTIIIOATES CROSS-REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of copending application Serial No. 810,383, filed March 25, 1969, now abandoned.

FIELD OF INVENTION This invention is directed to O-alkyl-S-aliphatic hydrocarbyl-N-acylphosphoroamidothioates and S- alkyl-S-aliphatic hydrocarbyl-N- acylphosphoroamidodithioates and their use as insecticides.

BACKGROUND OF INVENTION U.S. Pat. No. 3,309,266 teaches that O-alkyl-S-alkyl phosphoroamidothioates are insecticidal. The phosphoroamidothioates of this patent exhibit both contact and systemic activity against a variety of insects.

Like many of the phosphate insecticides the phosphoroamidothioates of U.S. Pat. No. 3,309,266 are toxic to mammals at fairly low dosages. For instance the LD oral toxicity of O-methyl-S-methyl phosphoroamidothioate as established by tests on laboratory animals is about mg./kg. This toxicity decreases the commercial potential of the phosphoroamidothioates of U.S. Pat. No. 3,309,266 substantially. It may even preclude their use in certain environments.

DESCRIPTION OF INVENTION wherein:

R is alkyl of one to three carbon atoms,

R is an aliphatic hydrocarbyl radical of one to three carbon atoms,

R is hydrogen or alkyl of one to three carbon atoms,

X is carbonyl or sulfonyl,

Y is oxygen or sulfur, and

a. when X is carbonyl R is hydrogen, alkyl of one to 18 carbon atoms, haloalkyl of one to 18 carbon atoms and one to fourhalogens of atomic number 9 to 35 (fluorine, chlorine and bromine), alkenyl of two to 18 carbon atoms, alkynyl of three to 18 carbon atoms, cycloalkyl of three to eight carbon atoms, a heterocyclic radical of l hetero oxygen, sulfur or nitrogen atom and four to five annular carbon atoms and a total of four to eight carbon atoms, alkoxyalkyl of two to 12 carbon atoms, alkylthioalkyl of two to 12 carbon atoms, alkoxy of one to 12 carbon atoms, alkylthio of one to 12 carbon atoms, phenyl, phenyl substituted with one or two alkyl radicals of one to three carbon atoms, alkoxy radicals of one to three carbon atoms, halogen atoms of atomic number nine to 35 or nitro groups, styryl, phenylalkyl in which the alkyl is of one to three carbon atoms, phenoxyalkyl in which the alkyl is of one to three carbon atoms, thiophenoxyalkyl in which the alkyl is of one to three carbon atoms (as well as phenylalkyl, phenoxyalkyl and thiophenoxyalkyl in which the alkyl is of one to three carbon atoms substituted on the aromatic moiety with halogen atoms of atomic number nine to 35 or nitro groups) or mononitroalkyl of one to three carbon atoms; and

. when X is sulfonyl R is alkyl of one to 10 carbon atoms, cycloalkyl of three to eight carbon atoms or phenyl.

R will be alkyl, alkenyl or alkynyl. Such aliphatic hydrocarbyl radicals are methyl, ethyl, propyl, ally] and propargyl. If R is an unsaturated radical, it will normally have a single terminal olefinic or acetylenic site of unsaturation. The propyl groups represented by R and R may be either normal or iso.

R will be hydrogen, methyl, ethyl, propyl, isopropyl or cyclopropyl.

The following are illustrative of the radicals represented by R when X is carbonyl: Aliphatic and cycloaliphatic: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, amyl, heptyl, 3-ethylamyl, Z-meth'ylhexyl, n-hexyl, n-octyl, 4-methylheptyl, n-nonyl, n-decyl, 5- ethyloctyl, n-undecyl, n-dodecyl, S-methyldecyl, ntridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-

heptadecyl, n-octadecyl, chloromethyl, dichloromethyl, bromomethyl, 2-chloroethyl, 1,2- dichloroethyl, 8,9-dichloropentadecyl, 2-bromo-2- chloroethyl, trifluoromethyl, 3-chloro-propyl, 2,4,6- trichlorohexyl, 3,5-dibromoamyl, 7-chloroheptyl, 3chloro-5,6-dibromoocytly, 2,2-difluoroethyl, llbromododecyl, vinyl, propenyl, 3butenyl, 2butenyl, 4- pentenyl, 4-hexenyl, S-hexenyl, S-heptenyl, 3-heptenyl, 4-octenyl, 7-octenyl, 5-nonenyl, 4-nonenyl, 7-nonenyl, 9-decenyl, 6-decenyl, ll-dodecenyl, 8-undecenyl, 8- pentadecenyl, S-heptadecenyl, S-heptadecenyl, l0-

heptadecenyl, 8,1 l-heptadecyldieneyl, 8,1 l,l4-heptadecyltrieneyl, propargyl, S-heptadecinyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,

yl, 2-chloro-4-methyl-phenyl, p-fluorophenyl, m-

fluorophenyl, p-bromophenyl, 2-fluoro-4-chlorophenyl, 3-methoxyphenyl-2-chloro-4-propylphenyl 4-ethoxyphenyl, m and p-nitrophenyl, Z-chloro-S- nitrophenyl, benzyl, phenylethyl, phenypropyl, phenoxymethyl, phenoxyethyl, phenoxypropyl, thiophenoxymethyl, thiophenoxyethyl, thiophenoxypropyl, 2,4-dinitrophenyl, 3,5-dinitrophenyl.

Heterocyclic: Z-pyridyl, 3-lutidyl, Z-pyrollyl, 2-thienyl, Z-furfuryl, Z-furylvinyl, 3-tetrahydrofurfuryl.

Included among the radicals represented by R when X is sulfonyl are: methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, amyl, hexyl, heptyl, S-methylhexyl, octyl, nonyl, decyl, cyclo-propyl, cyclobutyl, cyclohexyl, cyclooctyl and phenyl.

Preferred phosphoroamidothioates of this invention are those wherein R and R are methyl or ethyl, more preferably methyl, R is hydrogen and the organic radicals represented by R individually have a maximum of carbon atoms. Particularly preferred are those in which R and R are methyl, R is hydrogen, X is carbonyl, Y is oxygen, and R is alkyl, more preferably straight-chain alkyl, of one to 10 carbon atoms.

Representative compounds of the above formula are: O-methyl-S-methyl-N-formylphosphoroamidothioate, O-methyl-S-methyl-n-acetylphosphoroamidothioate, O-methyl-S-methyl-N-methyl-N- acetylphosphoroamidothioate, O-methyl-S-methyl-N- propionylphosphoroamidothioate, O-methyl-S-methyl- N-butyrylphosphoroamidothioate, O-methyl-S-methyl- N-isobutyrylphosphoroamidothioate, O-methyl-S- methyl-N-pentanoylphosphoroamidothioate, Q- methyl-S-methyl-N-hexanoylphosphoroamidothioate, O-methyl-S-methyl-N-heptanoylphosphoroamidothioate, O-methyl-S-methyl-N- methyl-N-octanoylphosphoroamidothioate, O-methyl- S-methyl-N-decanoylphosphoroamidothiate, O- methyl-S-methyl-N- dodecanoylphosphoroamidothioate, O-methyl-S- methyl-N-chloroacetylphosphoroamidothioate, O- methyl-S-methyl-N- bromoacetylphosphoroamidothloate, O-methyl-S- methyl-N-3-chlorobutyrylphosphoroamidothioate, O- methyl-S-methyl-N-Isbromopropionylphosphoroamidothioate, O-methyl-S-methyl-N-3,3- dichloropropionylphosphoroamidothioate, O-methyl- S-methyl-N-methyl-N- dichloroacetylphosphoroamidothioate, O-methyl-S- methyl- N-trifluoroacetylphosphoroamidothipate, 0- methyl-S-methyl-N-2, 3,4-trichloropentanoylphosphoroamidothioate, O-methyl-S-methyl-N- 3,4-dichlorobutyrylphosphoroamidothioate, O-methyl- S-methyl-N-3,3-difluoropropionylphosphoroamidothioate, O-methyl-S-methyl-N- fluoroacetylphosphoroamidothloate, O-methyl-S- methyl-N-7-bromoheptanoylphosphoroamidothioate, O-methyl-S-methyl-N-methyl-N-6,G-dibromohexanoylphosphoroamidothioate, O-methyl-S-methyl-N- 2,4-dichloro-6-bromohexanoylphosphoroamidothioate, O-methyl-Smethyl-N-8- chlorooctanoylphosphoroamidothioate, O-methyl-S methyl-N-2,6-dibromooctanoylphosphoroamidothioate, O-methyl-S-methyLN- l2-chlorododecanoylphosphoroamidothioate, O- methyl-S-methyl-acrylylphosphoroamidothloate, O- methyl-,S-methyl-N-Zi-butenoylphosphoroamidothioate, O-methyl-S-methyl-N- isobutenoylphosphoroamidothioate, O-methyl-S- methyl-N-methyl-N-Zl-pentenoylphosphoroamidothioate, O-methyl-S-methyl-N- 4-pentenoylphosphoroamidothloate, O-methyl-S- methyl-N-6-heptenoylphosphoroamidothioate, O- methyl-S-methyl-N-7-octenoylphosphoroamidothioate, O-methyl-S-methyl-N- 1 l-dodecenoylphosphoroamidothioate, O-methyl-S- methyl-N-cyclopropanoylphosphoroamidothioate, 0- methyl-S-methyl-N-methyl-N-cyclohexanoylphosphoroamidothioate, O-methyl-S-methyl-N- cyclohexanoylphosphoroamidothioate, O-methyl-S- methyl-N-cyclooctanoylphosphoroamidothioate.

O-methyl-S-methyl-N-3-pyridylcarbonylphosphoroamidothioate, O-methyl-S-methyl-N-Z-lutidylcarbonylphosphoroamidothioate, O-methyl-S- methyl-N-3-pyrollylcarbonylphosphoroamidothioate, O-methyl-S-methyl-N-2-thienylcarbonylphosphoroamidothioate, O-methyl-S-methyl-N-2-furoylphosphoroamidothioate, O-methyl-S-methyl-N-2- furylacrytoylphosphoroamidothioate. O-methyl-S-methyl-N-2-methoxyacetylphosphoroamidothioate, O-methyl-S-methyl-N- 2-pentoxyacetylphosphoroamidothioate, O-methyl-S- methyl-N-3-methoxypropionylphosphoromaidothioate O-methyl-S-methyl-N-4-ethoxybutyrylphosphoroamidothioate, O-methyl-S-methyl-N-L hexoxyacetylphosphoromaidothioate, O-methyl-S- methyl-N-4-propoxybutyrylphosphoroamidothioate, O-methyl-S-methyl-N-5-pentoxypentanoylphosphoroamidothioate, O-methyl-S-methyl-N- 8-methoxyoctanoylphosphoroamidothioate, O-methyl- S-methyl-N- l O-methoxyundecanoylphosphoroamidothioate, O-methyl-S-methyl- N-8-butoxyoctanoylphosphoroamidothioate, O- methyl-S-methyl-N-Z- methylthioacetylphosphoroamidothioate, O-methyl-S- methyl-N-Z-hexylthioacetylphosphoroamidothioate, O-methyl-S-methyl-N-3-butylthiopropionylphosphoroamidothioate, O-methyl-S-methyl-N-S- methylthiopentanoylphosphoroamidothioate, O- methyl-S-methyl-N-6-methylthiooctanoylphosphoroamidothioate, O-methyl-S-methyl-N- l l-methylthioundecanoylphosphoroamidothioate.

O-methyl-S-methyl-N-methoxycarbonylphosphoroamidothioate, O-methyl-S-methyl-N- isopropoxycarbonylphosphoroarnidothioate, O- methyl-S-methyl-N-pentanoxycarbonylphosphoroamidothioate, O-methyl-S-methyl-N-hexanoxycarbonylphosphoroamidothioate, O-methyl-S- methyl-S-methyl-N-hexanoxycarbonylphosphoroamidothioate, O-methyl-S-methyl-N-octanoxycarbonylphosphoroamidothioate, O-methyl-S- methyl-N-dodecanoxycarbonylphosphoroamidothioa te, O-methyl-S-methyl-N-methylthiocarbonylphosphoroamidothloate, O-methyl-S-methyl-N- propylthiocarbonylphosphoroamidothioate, O-methyl- S-methyl-N-hexylthiocarbonylphosphoroamidothioate, Omethyl-S-methyl-N-octylthiocarbonylphosphoroamidothioate, O-methyl-S-methyl-N- dodecylthiocarbonylphosphoroamidothioate.

O-methyl-S-methyl-N- benzoylphosphoroamidothioate, O-methyl-S-methyl- N-4-toluoylphosphoroamidothioate, O-rnethyl-S- methyl-N3 ,S-dimethylbenzoylphosphoroamidothioate, O-methyl-S-methyl- N-4-isopropylbenzoylphosphoroamidothioate, O- methyl-S-methyl-N-4- chlorobenzoylphosphoroamidothioate, O-methyl-S- methyl-N-2,4-dichlorobenzoylphosphoroamidothioate, O-methyl-S-methyl-N-2-phenylacetylphosphoroamidothioate, O-methyl-S-methyl- N-3-phenylpropionylphosphoroamidothioate, O- methyl-S-methyl-N-3-fluor0- bcnzoylphosphoroamidothioate, O-methyl-S-methyl- N-2-phenoxyacetylphosphoroamidothioate, O-methyl- S-methyl-N-3-phenoxypropionylphosphoroamidothioate, O-methyl-S-methyl-Z- phenylthioacetylphosphoroamidothioate, O-methyl-S- methyl-N8-nitropropionylphosphoroamidothioate, O- methyl-S-methyl-N-2-phenylthiopropionylphosphoroamidothioate, O-methyl-S-methyl-N-4- nitrobutynylphosphoroamidothioate, O-methyl-S- mEthyX-N-Z,4-dinitrobenzoylphosphoroamidothioate, O-ethyl-S-methyl-N-acetylphosphoroamidothioate, O-isopropyl-S-methyl-N- acetylphosphoroamidothioate, methyl-N 2-chlor0- 4bromobutyrylphosphoroamidothioate, O-propyl-S- methyl-N-isopropionylphosphoroamidothioate, O- methyl-S-ethyl-N-acetylphosophoroamidothioate, O- methyl-S-ethyl-N- dichloroacetylphosphoroamidothioate, O-ethyl-S- ethyl-N-4-bromobutyrylphosphoroamidothioate, O- ethyl-Sethyl-N-formylphosphoroamidothioate, O- ethyl-S-ethyl-N-acetylphosphoroamidothioate, O-

ethyl-S-ethyl-N-3-chloropropionylphosphoroamidothioate, O-ethyl-S-ethyl-N-3,4-

dibromobutyrylphosphoroamidothioate, O-ethyl-S- ethyl-N-hexanoylphosphoroamidothioate, O-ethyl-S- ethyl-N-decanoylphosphoroamidothioate, O-ethyl-S- ethyl-N-ddecanoylphosphoroamidothioate, O-ethyl- S-ethyl-N-trifluoroacetylphosphoroamidothioate, O- ethyl-S-ethyl-N-acrylphosphor0amidothioate, O-ethyl- S-ethyl-N-5-hexenyl-phosphoroamidothioate, O-ethyl- S-ethyi-N-8-nonenoylphosphoroamidothioate, O-ethyl- S-ethyl-N-l l-dodecenoy1phosphoroamidothioate, O- ethyl-S-ethyl-N- cyclopropanoyiphosphoroamidothioate, O-ethyl-S- ethyl-N-cyclohexanoylphosphoroamidothioate, O-

chlorobenzoylphosphoroamidothioate, O-ethyl-S- ethyl-N-4-propylbenzoylphosphoroamidothioate, O- ethyl-S-ethyl-N-2,4-

dinitrobenzoylphosphoroamidothioate, O-ethyl-S- ethyl-N-4-chl0robenzoylphosphoroamidothioate, O-

ethyl-S-ethyl-N-3-phenylpropionylphosphoroamidothioate, O-propyl-S-ethyl-N- acetylphosphoroamidothioate, O-isopmpyl-S-ethyl-N acetylphosphoroamidothioate, O-propyl-S-ethyl-N-butyrylphosphoroamidothioate, O-methyl-S-propyl-N- isobutyrylphosphoroamidothioate, O-methyl-S-propyl- N-acetylphosphoroamidothioate, O-methyl-S- isopropyl-N-dibromoacetylphosphoroamidothioate, O- methyl-S-propyl-N-4-chlorobutyrylphosphoroamidothioate, O-ethyl-S-propyl-N-2,3- dichloropropionylphosphoroamidothioate, O-ethyl-S- isopropyl-N-acetylphosphoroamidothioate,

O-propyl-S-propyl-N-formylphosphoroamidothioate, O-propyl-S-propyl-N- acetylphosphoroamidothioate, O-propyl-S-propyl-N- butyrylphosphoroamidothioate, O-propyl-S-propyl-N- 3-chlorobutyrylphosphoroamidothioate, O-propyl-S- propyl-N-Z,3-dibromopropionylphosphoroamidothioate, O-propyl-S-propyl-N- dichloroacetylphosphoroamidothioate, O-isopropyl-S- propyl-N-acetylphosphoroamidothioate, O-ethyl-S- allyl-N-2,3-dibrom0propionylphosphoroamidothioate, O-ethyl-S-allyl-N-chloroacetylphosphoroamidothioate, O-methyl-S-allyl-N-acetylphosphoroamidothioate, O- methyl-S-allyl-N-butyrylphosphoroamidothioate, O- isopropyl-S-allyl-N-acetylphosphoroamidothioate, O- ethyl-S-pr0pargyl-N-propionylphosphoroamidothioate and O-propyl-S-propargyl-N-2-chlorobutyrylphosphoroamidothioate.

O-methyl-S-methyl-N-methanesulfonylphosphoroamidothioate, O-methyl-S-methyl-N- propanesulfonylphosphoroamidothioate, O-methyl-S- methyl-N-hexanesulfonylphosphoroamidothioate, O- methyl-S-methyl-N-octanesulfonylphosphoroamidothioate, O-methyl-S-methyl-N- dodecanesulfonylphosphoroamidothioate, O-methyl-S- methyl-N-benzenesulfonylphosphoroamidothioate, O- methyl-S-methyl-N-cyclohexanesulfonylphosphoroamidothioate, O-methyl-S-methyl-N- cyclopropanesulfonylphosphoroamidothioate, O-ethyl- N-methanesulfonylphosphoroamidothioate, O-ethyl-S- ethyl-N-hexanesulfonylphosphoroamidothioate, O- ethyl-S-ethyl-N-dodecanesulfonylphosphoroamidothioate, O-ethyl-S-ethyl-N-cycloctanesulfonylphosphoroamidothioate, O-ethyl-S-ethyl- N-benzenesulfonylphosphoroamidothioate, O-propyl- S-propyl-N-methanesulfonylphosphoroamidothioate, O-propyl-S-propyl-N-hexanesulfonylphosphoroamidothioate, O-propyl-S-propyl-N- dodecanesulfonylphosphoroamidothioate, O-propyl-S- propyl-N-cyclooctanesulfonylphosphoroamidothioate, O-propyl-S-propyl-N-benzenesulfonylphosphoroamidothioate, O-methyl-S-alIyi-N- methanesulfonylphosphoroamidothioate, O-methyl-S- aHyi-Nyhexanesulfonylphosphoroamidothioate, O- methyl-S-allyl-N-dodecanesulfonylphosphoroamidothioate, cyclooctanesulfonyl-phosphoroamidothioate, methyl-S-allyl-N-benzenesulfonylphosphoroamidothioate, O-methyl-S-propargyl-N- methanesulfonylphosphoroamidothioate, O-methyl-S- propargyl-N-hexanesulfonylphosphoroamidothioate, O-methyl-S-propargyl-N-dodecanesulfonylphosphoi'oamidothioate, O-methyl-S-propargyl-N- cyclooctanesulfonylphosphoroamidothiate and O- methyl-S-propargyl-N-benzenesulfonylphosphoroamidothioate.

Other representative compounds of the above formula are: S,S-dimethyl-N-formylphosphoroamidodithioate, S,S-dimethyl-N- acetylphosphoroamidodithioate, S,S-dimethyl-N- O-methyl-S-allyl-N- O- methyl-N-acetylphosphoroamidodithioate, S,S- dimethyl-N-propionylphosphoroamidodithioate, S,S- dimethyl-N-butyrylphosphoroamidodithioate, S,S- dimethyl-N-isobutyrylphosphoroamidodithioate, S,S- dimethyl-N-pentanoylphosphoroamidodithioate, S,S- dimethyl-N-hexanoylphosphoroamidodithioate, S,S- dimethyl-N-heptanoylphosphoroamidodithioate, S,S- dimethyl-N-octanoylphosphoroamidodithioate, S,S- dimethyl-N-decanoylphosphoroamidodithioate, S,S-

S,S-dimethyl- S,S-

S,S-dimethyl-N- S,S-dimethyl- S,S-

S,Sdimethyl-N-2,6-

dibromooctanoylphosphoroamidodithioate, S,S- dimethyl-N-l2- chlorododecanoylphosphoroamidodithioate, S,S- dimethylacrylylphosphofoamidodithioate, S,S-

dimethyl-N-3-butenoylphosphoroamidodithioate, S,S- dimethyl-N-isobutenoylphosphoroamidodithioate, S,S- dimethyl-N-methyl-N-3-pentenoylphosphoroamidodithioate, S,S-dimethyI-N-4- pentenoylphosphoroamidodithioate, S,S-dimethyl-N-6- heptenoylphosphoroamidodithioate, S,S-dimethyl-N-7- octenoylphosphoroamidodithioate, S,S-dimethyl-N- 1 l1 l-dodecenoylphosphoroamidodithioate, S,S- dimethyl-N-cyclopropanoylphosphoroamidodithioate, S,S-dimethyl-N-methyl-N-cyclohexanoylphosphoroamidodithioate, S,S-dimethyl-N- cyclohexanoylphosphoroamidodithioate, S,S-dimethy]- N-cyclooctanoylphosphoroamidodithioate.

S,S-dimethyl-N-3-pyridylcarbonylphosphoroamidodithioate, S,S-dimethy!-N-2-lutidylcarbonylphosphoroamidodithioate, S,S-dimethyl-N-3- pyrollylcarbonylphosphoroamidodithioate, S,S- dimethyl-N-2-thienylcarbonylphosphoroamidodithioat e, S,S-dimethyl-N-2-furoylphosphoroamidodithioate, S,S-dimethyl-N-2-furylacryloylphosphoroamidodithioate.

S,S-dimethylN-2-meth0xyacetylphosphoroamidodithioate, S,S-dimethyl-N-2- pentoxyacetyiphosphoroamidodithioate, S,S-dimethyl- N-3-methoxypropionylphosphoroamidodithioate, S,S- dimethyl-N4-ethoxybutyrylphosphoroamidodithioate, S,S-dimethyl-N-2-hexoxyacetylphosphoroamidodithioate, propoxybutyrylphosphoroamidodithioate, dimethyl-N-S-pentoxypentanoylphosphoroamidodithioate, S,S-dimethyl-N-8- methoxyoctanoylphosphoroamidodithioate, S,S- dimethyl-N-lO-methoxyundecanoylphosphoroamidodithioate, S,S-dimethyl-N-8- butoxyoctanoylphosphoroamidodithioate, S,S- dimethyl-N-2-methylthioacetylphosphoroamidodithioa te, S,S-dimethyl-N-2-hexy!thioacetylphosphoroamidodithioate, S,S-dimethyl-N- 3-butylthiopropionylphosphoroamidodithioate, S,S- dimethyl-N-S-methylthiopentanoylphosphoroamidodithioate, methylthiooctanoylphosphoroamidodithioate, dimethyl-N-l l-methylthioundecanoylphosphoroamidodithioate.

S,S-dimethyl-N-methoxycarbonylphosphoroamidodithioate, S,S-dimethyl-N- isopropoxycarbonylphosphoroamidodithioate, S,S- dimethyl-N-pentanoxycarbonylphosphoroamidodithio ate, ylphosphoroamidodithioate, S,S-dimethyl-N-octanoxycarbonylphosphoroamidodithioate, S,S-dimethyl-N- dodecanoxycarbonylphosphoroamidodithioate, S,S- dimethyl-N-methylthiocarbonylphosphoroamidodithi oate, S,S-dimethyl-N-propylthiocarbonylphosphoroamidodithioate, S,S-dimethyl-N-hexylthiocarbonylphosphoroamidodithioate, S,S-dimethyl- N-octylthiocarbonylphosphoroamidodithioate, S,S- dimethyl-N-dodecylthiocarbonylphosphoroamidodith S,S-dimethyl-N-4- 8,8-

. ioate,

S,S-dimethyl-N-benzoylphosphoroamidodithioate, S,S-dimethyl-N-4-toluoylphosphoroamidodithioate, S,Sdimethyl-N-3,S-dimethylbenzoylphosphoroamidodithioate, S,S-dimethyl-N-4- isopropylbenzoylphosphoroamidodithioate, S,S- dimethyl-N-4-chlorobenzoylphosphoroamidodithioate, S,S-dimethyl-N-2,4- dichlorobenzoylphosphoroamidodithioate, S,S- dimethyl-N-Z-phenylacetylphosphoroamidodithioate, S,S-dimethyl-N-3-phenylpropionylphosphoroamidodithioate, S,S-dimethyl-N-3- fluorobenzoylphosphoroamidodithioate, S,S-dimethyl- N-2-phenoxyacetylphosphoroamidodithioate, S,S- dimethyl-N-3-phenoxypropionylphosphoroamidodithioate, S,S-dimethyl-2-phenylthioacetylphosphoroamidodithioate, S,S-dimethyl-N- 3-nitropropionylphosphoroamidodithioate, S,S- dimethyl-N-Z-phenylthiopropionylphosphoroamidodithioate, S,S-dimethyl N-4- S,S-dimethyl-N-6- S,S-dimethyl-N-hexanoxycarbom 9 nitrobutynylphosphoroamidodithioate, S,S-dimethyl- N-2,4-dinitrobenzoylphosphoroamidodithioate.

, S-ethyl-S-methyl-N-acetylphosphoroamidodithioate, S-isopropyl-S-methyl-N-acetylph osphoroamidodithioate, S-ethyl-S-methyl-N-isopropionylphosphoroamidodithioate, S,S-diethyl-N-formylphosphoroamidodithioate, S,S-diethyl-N-3,4- dibromobutyrylphosphoroamidodithioate, S,S-diethyl- N-dodecanoylphosphoroamidodithioate, S,S-diethyl- N-acrylphosphoroamidodithioate, S,S-diethyl-N-8- nonenoylphosphoroamidodithioate, S,S-diethyl-N- cyclohexanoylphosphoroamidodithioate, S,S-diethyl- N-3-thienoylphosphoroamidodithioate, S,S-diethyl-N- 3-butoxypropionylphosphoroamidodithioate, S,S- ethyl-N-7-methylthioheptanoylphosphoroamidodith ioate, S,S-diethyl-N-methoxycarbonylphosphoroamidodithioate, S,S-diethyl-N- dodecylthiocarbonylphosphoroamidodithioate, S,S- diethyl-N-4-propylbenzoylphosphoroamidodithioate, S,S-diethyl-N-3-phenylpropionylphosphoroamidodithioate, S-methyl-S-propyl-N- isobutyrylphosphoroamidodithioate, S-methyl-S- propyl-N-4-chlorobutyrylphosphoroamidodithioate, S- ethyl-S-propyl-N-Z,3-dichloropropionylphosphoroamidodithioate.

S,S-dipropyl-N-formylphosphoroamidodithioate, S,S-dipropyl-N-2,3-dibromopropionylphosphoroamidodithioate, S-isopropyl-S-propyl-N- acetylphosphoroamidodithioate, S-methyl-S-allyl-N- acetylphosphoroamidodithioate, S-ethyl-S-propargyl- N-propionylphosphoroamidodithioate.

S,S-dimethyl-N-methanesulfonylphosphoroamidodithioate, S,S-dimethyl-N-octanesulfonylphosphoroamidodithioate, S,S-dimethyl- N-cyclohexanesulfonylphosphoroamidodithioate, S,S- diethyl-N-hexanesulfonylphosphoroamidodithioate, S,S-diethyl-N-hexanesulfonylphosphoroamidodithioate S,S-diethyl-N-benzenesulfonylphosphoroamidodithioate, S,S-dipropyl-N- dodecanesulfonylphosphoroamidodithioate, S-methyl- S-allyl-N-methanesulfonylphosphoroamidodithioate, S-methyl-S-allyl-N-cyclooctanesulfonylphosphoroamidodithioate, S-methyl-S-propargyl-N' hexanesulfonylphosphoroamidodithioate and S- methyl-S-propargyl-N-benzenesulfonylphosphoroamidodithioate.

O-alkyl-S-aliphatic hydrocarbyl-N- acylphosphoroamidothioates and S-alkyl-S-aliphatic hydrocarbyl-N-acylphosphoroamidodithioates of the above formula may be prepared by acylating (which includes sulfonylating) an appropriate O-alkyl-S- aliphatic hydrocarbyl phosphoroamidothioate or S- alkyl-S-aliphatic hydrocarbyl phosphoroamidodithioate. This technique is especially applicable to the N-alkanoyl compounds in which the alkyl group of the alkanoyl radical of of 1 to 4 carbon atoms. As indicated previously, O-alkyl-S-alkyl phosphoroamidothioates and their preparation are dis closed in U.S. Pat. No. 3,309,266. O-alkyl-S-unsaturated aliphatic hydrocarbyl phosphoroamidothioates and their preparation are disclosed in copending application Ser. No. 486,233, filed Sept. 9, 1965, the disclosure of which is hereby incorporated by reference.

Conventional acylating agents, such as acyl halides, ketenes and acid anhydrides and conventional acylating conditions may be used in this reaction. In the case of the N-alkanoyl compounds alkanoyl chlorides are preferred acylating agents.

This acylation reaction (illustrated with an acyl halide as the acylating agent) may be represented by the following equation:

BY RY This acylation will usually be carried out at about 0 to 60 C. in the presence of solvents such as methylene chloride, chloroform, tetrahydrofuran and benzene. Pressure is not critical in this reaction. For convenience, atmospheric or autogenous pressure will be used. Under normal conditions, stoichiometric proportions or a slight deficiency of acylating agent will be used. The acylation will usually take 2 to 24 hours to reach completion. The reaction product may be purified by conventional extraction and recrystallization techniques.

N-acylated phosphoroamidothioates of this inven tion may also be prepared by acylating an appropriate 0,0-dialkyl phosphoroamidothionate and then reacting the resulting N-acyl phosphoroamidothionate with an alkylating (*alkylating is used generically and is intended to include agents which are used to incorporate alkenyl and alkynyl groups.) agent to produce the O- alkyl-S-aliphatic hydrocarbyl-N- acylphosphoroamidothioate. This reaction scheme is represented (using an acyl chloride as the acylating agent) by the following equation:

This acylation may be carried out by the same techniques described above for acylating O-alkyl-S- aliphatic hydrocarbyl phosphoroamidothioates. The reaction between the N-acylphosphoroamidothionate and the alkylating agent may be done according to the procedures described in U.S. Pat. No. 3,309,266 for reacting 0,0-dialkyl phosphoroamidothionate with an alkylating agent. In the case of the preferred compounds of this invention (i.e., R and R are methyl and R is hydrogen) dimethyl sulfate is the preferred alkylating agent.

If the acylating agent, e.g. R -XCl, is weak it may be desirable to prepare the compounds of this invention by amidating an appropriate 0,0-dialkyl phosphorothiochloridate to obtain 0,0-dialkyl-N- aoylphosph oroamidothioate and reacting said N-acyl phosphoroamidothioate with an alkylating agent as describe above. This reactionscheme is illustrated by the following set of equations:

The S-alkyl-S-aliphatic hydrocarbyl phosphoroamidodithioate can be prepared by the reaction of phosphorous oxychloride with a mercaptan followed by amidation of the resulting S-alkyl-S-aliphatic hydrocarbyl phosphoroamidodithioate. The first step of the synthesis involves the addition of 2 moles of a mercaptan to 1 mole of phosphorous oxychloride (POCl according to the following equations (if R arid R are the same, a single reaction can be carried out):

i O +RSH RS-P Gl+HC1 RISH P The above reactions are preferably carried out in the presence of a weak base, such as the organic amines, for example pyridine, dimethyl aniline, triethyl amine, etc. The base is preferably present inan amount at least equal to the moles of mercaptan. An inert organic solvent, such as diethyl ether, tetrahydrofuran, dioxane, dichloromethane, etc. may be present. The reaction temperatures are generally in the range of 0 to 15 C., preferably 0 to 5 C. The reaction time necessary to complete the addition of the mercaptan to the phosphorous oxychloride will range from about 1 to hours. The S-alkyl-S-aliphatic hydrocarbyl phosphorochloridodithioate product can be purified by distillation, crystallization or chromatography, if desired.

The second step of the preparation, i.e. amidlation, is carried out by adding gaseous ammonia to a solution of the S-alkyl-S-aliphatic hydrocarbyl phosphorochloridodithioate according to the following equation:

The reaction is preferably carried out in an inert organic solvent,.such as benzene, toluene, xylene and the like, at temperatures in the: range of 10 to C., preferably 40 to 60 C. Completion of the reaction is indicated by cessation of ammonium chloride precipitation. Following the reaction, the crude product can be isolated by filtration and then separated from ammonium chloride by selective extraction with a solvent, such as acetone, methanol of similar organic materials.

EXAMPLES vThe following examples describe methods which may be used to prepare the phosphoroamidothioates of this invention. These examples are not intended to limit the invention described herein. Percentages are by weight unless otherwise indicated.

EXAMPLE 1 acetylphosphoroamidothioate. This material melted at 64-68A C. and had the following analysis:

Calculated Found P 16.93 18.28 ats 17.43 18.05-

EXAMPLE 2 176 g. 1.25 moles) of O-methyl-S-methyl phosphoroamidothionate was dissolved in 300 ml. of dichloromethane and charged to a 1 liter flask. 98 g.

(1.25 moles) of acetylchloride dissolved in 100 m1. of I dichloromethane was added. The solution was stirred, warmed to 33 C., held at that temperature for 4 hours,.

then and additional 98 g. (1.25 moles) of acetylchloride was added. The mixture was held at room temperature for 18 hours and then added to 500 ml. of ice water. The phases were separated and the aqueous phase was extracted with 4 200 ml. portions of dichloromethane. The extracts were combined with the separated organic phase and the solvent removed by gentle heating under vacuum to give 50 g. of product. The aqueous phase after batch extraction was further extracted continuously for 18 hours in a liquid-liquid extraction apparatus using 2 liters of dichloromethane as the extractant. Evaporation of the dichloromethane gave an additional 1 10 g. of product, giving a total yield of 87 percent. Upon purification, the product, 0- methyl-Smethyl-N-acetylphosphoroamidothioate, gave the following analysis:

13 EXAMPLE 3 6 g. of 0,0-diethyl-N- acetylphosphoroamidothionate was mixed with 10 ml. ethyl iodide in a flask. This mixture was refluxed for 30 hours. The resulting reaction mixture was stripped at 80C., 30 mm. Hg leaving 4.5 g. oil which crystallized on standing. This material, O-ethyl-S-ethyl-N- acetylphosphoroamidothioate, had the following analysis:

Calculated Found EXAMPLE 4 Calculated Found N 8.9 9.65 S 41.0 38.1 P 19.7 19.2

S,S-dimethylphosphoroamidodithioate was dissolved in 250 ml. dichloromethane and charged to a 500 ml. flask. 39.3 g. (0.5 mole) of acetylchloride was added. The solution was refluxed for 2 hours and stored at room temperature for 18 hours. The dichloromethane and excess acetylchloride were removed by evaporation and the product dissolved in 250 ml. of dichloromethane to which was added 250 ml. water containing sufficient calcium hydroxide to give a pH of 7 after thorough mixing. The organic phase was separated from the aqueous phase and the 8,8- dimethyl-N-acetylphosphoroamidodithioate recovered from the organic phase as an oil (3.7 g.). Analysis was as follows:

Calculated Found N 7.03 6.48 S 32.1 31.05 P 15.52 14.08

Calculated Found 35 TABLE I Element analyses P 10.50 10.67 Percent P Percent S S 10.85 10.47 M.1.,

Compound 0. Found Cale. Found Cale.

4o O-ethyl-S-methyl-N-acetyl- 67 76 15.35 16. 70 16.95 16.24

phosphoroamidothioatm. O-ethyl-S-propargyl-N- EXAMPLE acetylphosphoroamidoothicttfielugnnfinffi on 14.05 13.31 15.53 14.35 S,S-dimethyl-N-acetylphosphoroamidodithioate was 335 5.; xyfgg g i prepared as f ll nor a nidon a te 95-100 12.33 12.18 12.75 13.40

met y-S-me y- A solutlon of 73.2 g. (0.48 mole) of phosphorous ox- 45 hutyrylphosphoroamidoychloride in 300 ml. of dry diethyl ether was charged to },,;",,f,- 1M8 '18 t plOplOllYlDllOSDhDrO- a 1 met flask at a tempel'aFure of O C A of amidothioate on 14.52 15.65 15.22 15. 76.2 g. (0.96 mole) of pyridine and 49 g. (1.0 mole) of O-rnethyl-S-methyl-N- isobutyrylphosphoromethyl mercaptan m 9 Ofdlethyl ether was addFd mnidothioute on 2,10 14, 3 13, 5 15.13 slowly to the flask containing phosphorous oxychlonde 5O g -p vg-gvdo 163K111 1O I D1111 over a 2-hour period of tlme, malntalmng the tempera- (hi0 011 2, 2, 1, 13,42 ture from 0 to 5C. The mixture was then stirred for an g gfggg gz g ggglgm additional 6 hours at temperatures of 0 to 10C. After Ophosphfgoamigoglgloate. 011 13.75 14.8 14.82 15.3 18 hours of standing at 0C. the crude reaction product ',?.E1., i i.3$h .5 was separated from the solid residue, stripped of solm gf; jgqigg Oil 11-90 1376 13-68 14-25 vent and purified to give 31.7 g of a liquid S,S- dgeanoylphosphoroamido- O1 67 10 m 47 10 85 t ioate i 10. drmethylphosphorochloridodrthroate. OmemyLsmemypN:

The above S,S-d1methylphosphorochloridodithloate 3 ;y gv phosp on 15 99 15 85 1Q 20 16 42 1108. e 1 c. was then charged with 500 ml. of toluene to a 1 liter omemynsflethynN- dichloroaeetylphosphoroflask angmonla gas added slowly at a temperature nmidgthioate 129-132 12.60 12,28 13.27 12.71 of 50 to C. When the temperature started to drop, o-n wtn i-s-gn tpy ammonia addition was l The reaclio" was held on 12.48 11.35 12. 35 12.35 at 50C. for one-half hour and then cooled to room temperature and filtered. The filtrate was stripped of 4.11111101111 0315...". w. 011 11.42 11.42 11.93 11.82

- O-methyl- -methylsolvent under vacuum, then purified to g1ve 6.6 g. of dinmmymrylpymhos S,S-d1methylphosphoroamldodrthloate. The compound phm'oflmldothwate I8 13-38 13-85 14-62 1433 a a O-n1etl1yl-S-1nethyl-N- had a melting po1nt of 103 -l05 C., and the following rotonylphosphoroan idothionte Oil 13.82 15.32

N, S, P analysis:

Many of the N-acylphosphoroamidothioates of this invention are more selective in their insecticidal activity than their non-acylated analogs. Thus, a given compound may be highly active against one insect species and relatively inactive against another. The preferred compounds of this invention are especially effective against roaches, houseflies, cabbage loopers, aphids, bollworm, armyworms and corn earworms. Representative phosphoroamidothioates of this invention were tested as follows to illustrate the insecticidal properties of this grouping. Test results are reported in Table I1.

TEST PROCEDURES Cabbage looper (Tric/mplusia nr'): An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to 250 ppm. Cabbage leaf sections were dipped in the toxicant solution and dried. The sections were then infested with cabbage looper larvae. Mortality readings were takenafter 24 hours.

German Cockroach (Blaitella germanica L): A 100 ppm acetone solution of the candidate toxicant was placed in a microsprayer (atomizer). A random mixture of anesthetized male and female roaches was placed in a container and 55 mg. of the above described acetone solution was sprayed on them. A lid was placed on the container. A mortality reading was made after 24 hours.

Two-spotted Mites (Tetramuchus urticae): An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to 100 ppm. Pinto bean leaves which were infested with mites were dipped in the toxicant solution. Mortality readings were taken after 24 hours.

Aphids (Aphis gossypii Glover): An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to 30 ppm. Cucumber leaves infested with the cotton aphids were dipped in the toxicant solution Mortality readings were then taken after 24 hours.

TABLE II O-ethyl-S-propargyl-N- acetylphosphoroamidothioate gave 93 percent mortality in tests on houseflies at a concentration of 125 ppm. using the above-described method.

In tests carried out in the field, O-methyl-S-methyl- N-acetylphosphoroamidothioate showed excellent activity against the following insects:

lnsect Crop Pea aphid alfalfa Western yellow striped armyworm alfalfa Beet arrnyworm alfalfa Lygus hesperus alfalfa Citrus snow scale citrus (grapefruit) Diamondback larvae collards Bullworm cotton Beet nrmyworm cotton Grccn peach aphid potatoes Beet nrmyworm sorghum Beet armyworm soybean Corn eat-worm corn As previously indicated the toxicological properties of the compounds of this invention are unexpectedly better than corresponding non-acylated compounds. This feature may be illustrated by comparing the toxicity index of a representative compound of this invention with that of its corresponding non-acylated analog. Toxicity index is a measure of a compounds safety relative to its insecticidal activity. it is defined here as:

LDgo insects (ppm )ILD rats-oral (mg/Kg.)

Compound Percent mortality O'methyl-S-methyl-N-acetylphosphoroamldothioate O-ethyl-S-methyl-Nacetylphosphoroamidothioate- 0-methyl-S-methyl-N-propionylphosphoroamidothioat 0-methyl-S-methyl-N-butyrylphosphoroamidothioatc. O S-dimethyl-N -isobutyrylphosphoroamidothioatc. O,S-dimethyl-N-h exanoylphosphoroamidothioatc 0 ,S-dimethyl-N-cyclopropaneearbonylphosphoroamidothioate O ,S-dimethyl-N-pivaloylphosphoroamidothloate O ,S-dimethyl-N -decanoylphosphoroamidothioate O,S-dimethyl-N-acryloylphosphoroamidothioate O,S-dimethyl-N-dichlornacetylphosphoroamidothioatc.

S,S-dlmethyl-N-acotylphosphoroamidoditllioate a German. p.p.m. concentration.

"500 p.p.m. concentration. 

1. A compound of the formula wherein R is alkyl of one to three carbon atoms, R1 is an aliphatic hydrocarbyl radical of one to three carbon atoms, R2 is hydrogen or alkyl of one to three carbon atoms, X is carbonyl, Y is oxygen or sulfur, R3 is hydrogen, alkyl of one to 18 carbon atoms, alkenyl of 2 to 18 carbon atoms, or alkynyl of three to 18 carbon atoms.
 2. The compound of claim 1 wherein R2 is hydrogen.
 3. The compound of claim 2 wherein R1 is alkyl or alkenyl, R3 is alkenyl and Y is oxygen.
 4. The compound of claim 3 wherein R3 is vinyl.
 5. The compound of claim 2 wherein R1 is alkyl or alkenyl and R3 is alkyl.
 6. The compound of claim 5 wherein Y is oxygen.
 7. The compound of claim 6 wherein R3 is straight chain alkyl of one to 10 carbon atoms.
 8. The compound of claim 7 wherein R and R1 are methyl or ethyl.
 9. The compound of claim 8 wherein R3 is methyl or ethyl.
 10. The compound of claim 2 wherein R1 is alkyl or alkenyl and R3 is hydrogen.
 11. The compound of claim 10 wherein R and R1 are methyl. 